SILICONE COMPOSITIONS AND THEIR USE IN CONTROLLING THE RELEASE OR TRANSFER OF PRINTED OR MOLDED PATTERNS AND TRANSFERRING PROCESSES THEREFORE

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EP 1 699 889 B1

(12)	EUROPEAN PATENT SPECIFICATION

(45)	Mention of the grant of the patent:
	08.09.2010 Bulletin 2010/36

(21)	Application number: 04810019.2

(22)	Date of filing: 22.10.2004

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International Patent Classification (IPC):

C09D 183/04^(2006.01)

B32B 27/08^(2006.01)

(86)	International application number:
	PCT/US2004/035251

(87)	International publication number:
	WO 2005/068569 (28.07.2005 Gazette 2005/30)

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SILICONE COMPOSITIONS AND THEIR USE IN CONTROLLING THE RELEASE OR TRANSFER OF PRINTED OR MOLDED PATTERNS AND TRANSFERRING PROCESSES THEREFORE

SILICONZUSAMMENSETZUNGEN UND DEREN VERWENDUNG BEI DER GEZIELTEN ABLÖSUNG ODER ÜBERTRAGUNG VON GEDRUCKTEN ODER GEFORMTEN STRUKTUREN UND ÜBERTRAGUNGSVERFAHREN DAFÜR

COMPOSITIONS DE SILICONE ET UTILISATION DE CELLES-CI POUR COMMANDER L'EDITION OU LE TRANSFERT DE MOTIFS IMPRIMES OU MOULES ET PROCESSUS DE TRANSFERT A CET EFFET

(84)	Designated Contracting States:
	AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

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Priority:

22.12.2003 US 531759 P

(43)	Date of publication of application:
	13.09.2006 Bulletin 2006/37

(73)	Proprietor: Dow Corning Corporation
	Midland, MI 48686-0994 (US)

(72)	Inventors:
	EKELAND, Robert Midland, MI 48642 (US) KATSOULIS, Dimitris Midland, MI 48642 (US) ZHU, Bizhong Midland, MI 48640 (US)

(74)	Representative: Russell, Lindsey et al
	Elkington and Fife LLP Thavies Inn House 3-4 Holborn Circus London EC1N 2HA London EC1N 2HA (GB)

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References cited: :

DENG, WU, SCOTT, BRITTAIN, WHITESIDES: "Prototyping of Masks, Masters, and Stamps/Molds for Soft Lithography Using an Office Printer and Photographic Reduction" ANAL. CHEM., vol. 72, no. 14, 2000, pages 3176-3180, XP002324934
WHITESIDES, STROOCK, GITLIN: "Components for integrated poly(dimethylsiloxane) microfluidic systems" ELECTROPHORESIS, vol. 23, 2002, pages 3461-3473, XP002324935

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).

Description

[0001] The present invention relates to silicone compositions that can be used to control the interface at which release occurs when a bi-layer or multi-layer structure comprising compositions as separate layers, and a pattern of a different material sandwiched in between, is separated. The present invention further relates to a process that utilizes these compositions to control the transfer or release of patterns deposited on a substrate.

[0002] In many patterning processes controlled release at a specific interface is desired so that the type and location of the patterns produced in or on the substrate can be controlled. Examples of application include most soft lithography processes to fabricate microfluidic devices, where upon curing, a polydimethylsiloxane has to release at a pre-determined interface so the shape, size, and location of the micro channels can be controlled.

[0003] The Decal Transfer Microprinting method was disclosed by William R Childs and Ralph G. Nuzzo in an article entitled "Decal transfer microlithography: A new soft-lithographic patterning method" in the Journal of the American Chemical Society, 124(45), pp. 13553-13596 (2002). In that article, Childs and Nuzzo disclose a polydimethylsiloxane pattern formed on a backing layer, and the pattern was eventually transferred to a substrate permanently by engineered adhesion and release. Such adhesion and release was achieved by heat and/or ultraviolet ozone treatment. The nature of ultraviolet ozone treatment is such that environmental exposure conditions are important variables in this process. The essential feature of this process is the controlled release at a specific interface. It is desirable to have a system that does not need heat or ultraviolet ozone treatment to engineer release at a specified interface.

[0004] Capillary micro contact printing used to pattern a conductive polymer polyaniline was disclosed by Weng Sing Beh, In Tae Kim, Dong Qin, Younan Xia, and George M. Whitesides in an article entitled "Formation of patterned microstructures of conducting polymers by soft lithography and applications in microelectronic device fabrication", Advanced Materials, 11 (12), pp. 1038-1041 (1999). This article discloses a relief pattern formed on a polydimethylsiloxane surface by molding over a master and the polydimethylsiloxane was placed on a substrate to form a channel network. When a polyaniline emeraldine base in NMP was placed at the open end of the channels the solution was drawn into the channels by capillary force. Upon solvent evaporation, drying, and removal of the polydimethylsiloxane mold, the polyaniline emeraldine was converted to a conductive polyaniline emeraldine salt by doping with HCl. In this process the given nature of polydimethylsiloxane to release from the polyaniline surface and the substrate surface makes fabricating the circuit on the substrate possible. Processes such as this, however, do not have the freedom to easily switch between release at the interface of polydimethylsiloxane and polyaniline, and release at the interface between the polyaniline and the substrate.

[0005] Deng et al. discloses a release process in an article entitled "Prototyping of masks, masters, and stamps/molds for soft lithography using an office printer and photographic reduction", Analytical Chemistry, 72(14), pp. 3176-3180 (2000). The process disclosed uses a low cost, office laser printer in combination with CAD software to print a pattern onto paper. Photo reduction of the pattern by imaging it onto a 35 mm film or microfiche was used to obtain a master to mold polydimethylsiloxane. The polydimethylsiloxane releases from the film and from the developed image, replicating the patterns, and was used as stamps and molds for soft lithography processes.

[0006] Bottari in U.S. Patent No. 6,280,552 discloses the use of controlled release of printed edge electrodes to a touch screen panel. In this process the electrode was printed onto decal paper and covered with an over coat. The decal paper was removed and the electrode was transferred to the touch screen.

[0007] In all these processes, release occurs at one specific interface pre-determined by the material composition. Some of the release mechanisms have to be triggered by exposure to heat or ultraviolet light, some of them rely on the different surface properties of drastically different materials. The reverse of these processes, for example, releasing from a polyaniline/substrate interface to provide an embedded conductive pathway in the molding polymers on top of the substrate, instead of releasing from a polydimethylsiloxane/polyaniline interface to deposit it on the surface of the substrate, would require drastic change in materials, and thus change in other properties.

[0008] Consequently there is a need for better, more convenient, and reversible control of release or transfer of patterns placed between a substrate and a polymer molded on top of the substrate when the molded polymer and substrate are separated. It is desired that such control can be achieved with minimum change of mechanical, optical, electrical, and other properties of the substrate and molding polymers.

[0009] This invention relates to silicone compositions and a process to control the transfer of a printed or molded pattern. When a pattern of a third material is generated and placed in between such cured silicone compositions, interfacial release will occur only on the interface between the pattern and one composition of the pair when the pair is separated. This allows a clean control of whether the surface feature of a pattern will be replicated with high fidelity, or the pattern will be cleanly transferred from the surface of one composition to the other. Those familiar with the electronics, microfluidics, and optic device fabrication processes will appreciate the utility of such a process, enabled by the compositions, to build economically functional electrical and optical circuits, embedded three dimensional structures, two and three dimensional channel networks, and so on. The compositions are predominantly silicone based, and especially so when the variations of other properties need to be minimized. But organic polymers can also be included in them.

[0010] Thus this invention relates to a silicone coating composition comprising:

(I) a first coating layer comprising a silicone composition (X) obtained by a method comprising reacting:

(A) 100 parts by weight of at least one organosiloxane compound containing an average of greater than two alkenyl groups per molecule and having less than 1.5 mol % of silicon-bonded hydroxy groups wherein the organosiloxane compound is selected from
1. (i) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0,
2. (ii) an organosiloxane compound comprising R²₃SiO_1/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0,
3. (iii) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 and R¹SiO_3/2 units combined to SiO_4/2 units is from 4 to 99,
4. (iv) an organosiloxane compound comprising R²3SiO_1/2 units, R¹SiO_3/2 units, and R²₂SiO_2/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 units and R¹SiO_3/2 units combined to R²₂SiO_2/2 units is from 0.5 to 99,
5. (v) an organosiloxane compound comprising R²₂SiO_2/2 units and
  R¹SiO_3/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R¹SiO_3/2 units is from 0.2 to 4.0,
6. (vi) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R²₃SiO_1/2 units is from 0 to 15,000, and
7. (vii) an organosiloxane compound comprising R²₂SiO_2/2 units,
  R²₃SiO_1/2 units, and SiO_2/2 units, wherein the molar ratio of SiO_2/2 units to R²₂SiO_2/2 units and R²₃SiO_1/2 units combined is from 0.005 to 0.125
  wherein R¹ is a hydrocarbon group free of aliphatic unsaturation and R² is selected from R¹ and alkenyl groups;
(B) at least one organohydrogensilicon compound in an amount sufficient to crosslink (A) selected from
1. (i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H wherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴ is a divalent hydrocarbon group and
2. (ii) an organohydrogensiloxane compound having the formula
  (HR³_aSiO_(3-a)/2)b(R¹_cSiO_(4-c)/2)_d wherein R¹ and R³ are as defined above,
  1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;
(C) a catalytic amount of a hydrosilylation catalyst; and
optionally (D) an inorganic filler; and

(II) a second coating layer in contact with the coating layer (I), the second coating layer comprising a silicone composition (Y) obtained by a method comprising reacting:

(A') 100 parts by weight of at least one organosiloxane compound containing an average of greater than two alkenyl groups per molecule and having less than 1.5 mol % of silicon-bonded hydroxy groups, wherein the organosiloxane compound is selected from
1. (i) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units and R²₃SiO_1/2 units is from 0 to 15,000 and
2. (ii) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0 wherein R² is selected from hydrocarbon groups free of aliphatic unsaturation and alkenyl groups;
(B') at least one organohydrogensilicon compound in an amount sufficient to crosslink (A') selected from
1. (i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H and
2. (ii) an organohydrogensiloxane compound having the formula
  (HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d
wherein R¹ and R³ are each independently a hydrocarbon group free of aliphatic unsaturation, R⁴ is a divalent hydrocarbon group, 1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;
(C') a catalytic amount of a hydrosilylation catalyst; and optionally (D') an inorganic filler with the proviso that the molar ratio of R²₂SiO_2/2 units to all other units combined is higher in composition (Y) than in composition (X), and the surface energy of composition (Y) is lower than composition (X).

[0011] "Reacting" as used herein means mixing components (A)-(C) and (A')-(C'), respectively, and any optional components at room temperature (20-25°C) or heating a mixture comprising components (A')-(C'), and any optional components to temperatures above room temperature such as at temperatures of up to 200°C. Compositions (X) and (Y) may be prepared by mixing (or mechanically agitating) components (A)-(C) and (A')-(C'), respectively, and any optional components, to form a homogenous mixture. This may be accomplished by any convenient mixing method known in the art exemplified by a spatula, mechanical stirrers, in-line mixing systems containing baffles and/or blades, powered in-line mixers, homogenizers, a drum roller, a three-roll mill, a sigma blade mixer, a bread dough mixer, and a two roll mill. The order of mixing is not considered critical. Components (A)-(C) and (A')-(C') and any optional components, may be pre-mixed and applied or mixed during application if tack free time is short.

[0012] In compositions (X) and (Y) above, the hydrocarbon groups free of aliphatic unsaturation are illustrated by alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, and aryl groups such as phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl. The hydrocarbon group free of aliphatic unsaturation is typically methyl. The alkenyl groups in compositions (X) and (Y) above are illustrated by vinyl, allyl, butenyl, pentenyl, hexenyl, and decenyl. The alkenyl group is typically vinyl. The divalent hydrocarbon groups in compositions (X) and (Y) above are illustrated by alkylene groups selected from -(CH₂)_x- where x has a value of 2 to 10, -CH₂CH(CH₃)-, -CH₂CH(CH₃)CH₂-, and -CH₂CH₂CH(CH₂CH₃)CH₂CH₂CH₂-.

[0013] Component (A) is typically illustrated by an organosiloxane compound comprising ViMe₂SiO_1/2 units and PhSiO_3/2 units, where the molar ratio of ViMe₂SiO_1/2 units to PhSiO_3/2 is from 0.05 to 3.0. Component (A) is illustrated by an organosiloxane having the formula (ViMe₂SiO_1/2)₂₅(PhSiO_3/2)₇₅.

[0014] Component (B) is typically illustrated by an organohydrogensilane compound having the formula HMe₂Si-Ph-SiMe₂H.

[0015] Component (A') is typically illustrated by an organosiloxane comprising (ViMe₂SiO_1/2) units, (Me₃SiO_1/2) units, (Me₂SiO_2/2) units, and (SiO₂) units wherein the ratio of (ViMe₂SiO_1/2) units + (Me₃SiO_1/2) units to (Me₂SiO_2/2) units, is from 1/10000 to 1/5 and the ratio of (Me₂SiO_2/2) units to (SiO₂) units is from 200/1 to 1/4. Component (A') is illustrated by an organosiloxane compound having the formula (ViMe₂SiO_1/2)₂(Me₃SiO_1/2)₁₅(Me₂SiO_2/2)₈₁(SiO₂)₂₂.

[0016] Component (B') is typically illustrated by an organohydrogensiloxane compound having the formula Me₃SiO(Me₂SiO)_x(MeHSiO)_ySiMe₃ wherein the value of x+y provides a molecular weight of 134 to 75,000 and there are at least two SiH groups per molecule. Component (B') is illustrated by an organosiloxane compound having the formula Me₃SiO(Me₂SiO)₃(MeHSiO)₅SiMe₃.

[0017] Components (C) and (C'), the hydrosilylation catalysts are illustrated by any metal-containing catalyst which facilitates the reaction of silicon-bonded hydrogen atoms of components (B) and (B'), respectively, with the silicon-bonded alkenyl groups of components (A) and (A'), respectively. The metals are illustrated by ruthenium, rhodium, palladium, osmium, iridium, or platinum.

[0018] The metal-containing catalyst is typically a platinum-containing catalyst since they are the most widely used and available and because they provide a more favorable effect for the compositions of this invention in terms of improved reaction rates. Platinum-containing catalysts can be a compound or complex of a platinum metal.

[0019] One type of typical platinum-containing catalyst in the compositions of this invention is the composition that is obtained when chloroplatinic acid is reacted with an aliphatically unsaturated organosilicon compound such as divinyltetramethyldisiloxane, because of its easy dispersibility in organosilicon systems.

[0020] Preferably components (C) and (C') are selected from chloroplatinic acid, alcohol modified chloroplatinic acids, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and divinyltetramethyldisiloxane, fine platinum particles adsorbed on carbon carriers, platinum supported on metal oxide carriers such as Pt(Al₂O₃), platinum black, platinum acetylacetonate, platinum(divinyltetramethyldisiloxane), platinous halides exemplified by PtCl₂ and PtCl₄, Pt(CN)₂, complexes of platinous halides with unsaturated compounds exemplified by ethylene, propylene, and organovinylsiloxanes, styrene hexamethyldiplatinum, and RhCl₃(Bu₂S)₃.

[0021] The amount of hydrosilylation catalyst that is used is not narrowly limited as long as there is a sufficient amount to accelerate a reaction between Components (A) and (B), and between Components (A') and (B'), at room temperature or at temperatures above room temperature. The exact necessary amount of this catalyst will depend on the particular catalyst utilized and is not easily predictable. However, for platinum-containing catalysts the amount can be as low as one weight part of platinum for every one million weight parts of components (A) + (B) or components (A') + (B'). The catalyst can be added at an amount 10 to 120 weight parts per one million parts of components (A) + (B) or (A') + (B'), but is typically added in an amount from 10 to 60 weight parts per one million parts of components (A) + (B) or components (A') + (B').

[0022] Component (D) and (D'), the inorganic filler, is an optional component which may be added to Compositions (X) and/or (Y). The inorganic filler is illustrated by hollow microsperes, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, ground quartz, calcium carbonate, magnesium carbonate, diatomaceous earth, wollastonite, calcined clay, clay, talc, kaolin, titanium oxide, bentonite, ferric oxide, zinc oxide, glass balloon, glass beads, mica, glass powder, glass balloons, coal dust, acrylic resin powder, phenolic resin powder, ceramic powder, zeolite, slate powder, organic fibers, and inorganic fibers. The amount of inorganic filler is typically in an amount from 5 to 30 per 100 parts of component (A).

[0023] This invention also relates to a method of making an article of manufacture comprising the steps of: (I) applying silicone composition (Y) to a substrate to form a coating 1 to 500 micrometer thick; (II) curing the silicone composition of step (I); (III) forming a pattern on top of the product of step (II); (IV) applying silicone composition (X) over the pattern of step (III); (V) curing silicone composition (X) with the proviso that the molar ratio ofR²₂SiO_2/2 units to all other units combined is higher in silicone composition (Y) than in the silicone composition (X), and the surface energy of the cured composition (Y) is lower than the cured silicone composition (X); and (VI) separating the cured silicone composition (X) of step (V) from the substrate.

[0024] Upon separation the pattern will be transferred and embedded into the cured composition (X). The separation between the two silicone compositions, and between the silicone composition (Y) and the pattern of step (III), is clean.

[0025] In the above method, compositions (X) and (Y) are as described above. Curing of the silicone compositions in the above method is typically accomplished by exposing the composition to temperatures ranging from 25 to 150°C, and more typically from 60 to 100°C. The method of applying the silicone composition is not critical to the present invention and can be any of those known in the art for applying liquid coatings to substrates. The silicone composition in the above method can be applied by such methods as dipping, spraying, wiping, brushing, extrusion, and coextrusion. The substrate to which the silicone composition is applied can be any solid substrate such as glass, metal, or plastic.

[0026] When the surface profile of the pattern needs to be replicated and minimum or no transfer of the pattern into the molding layer is desired, the process can be reversed. In this case the silicone composition (X) is used as the coating, and the silicone composition (Y) will be the molding composition used on top of the coating. Thus this invention also relates to a method of making an article of manufacture comprising the steps of:

(I) applying a silicone composition (X) to a substrate to form a coating 1 to 500 micrometer thick wherein silicone composition (X) is obtained by a method comprising reacting:

(A) 100 parts by weight of at least one organosiloxane compound containing an average of greater than two alkenyl groups per molecule and having less than 1.5 mol % of silicon-bonded hydroxy groups wherein the organosiloxane compound is selected from
1. (i) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0,
2. (ii) an organosiloxane compound comprising R²₃SiO_1/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹ SiO_3/2 units is from 0.05 to 3.0,
3. (iii) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 and R¹SiO_3/2 units combined to SiO_4/2 units is from 4 to 99,
4. (iv) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and R²₂SiO_2/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 units and R¹SiO_3/2 units combined to R²₂SiO_2/2 units is from 0.5 to 99,
5. (v) an organosiloxane compound comprising R²₂SiO_2/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R¹SiO_3/2 units is from 0.2 to 4.0,
6. (vi) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R²₃SiO_1/2 units is from 0 to 15,000, and
7. (vii) an organosiloxane compound comprising R²₂SiO_2/2 units,
  R²₃SiO_1/2 units, and SiO_2/2 units, wherein the molar ratio of SiO_2/2 units to R²₂SiO_2/2 units and R²₃SiO_1/2 units combined is from 0.005 to 0.125
  wherein R¹ is a hydrocarbon group free of aliphatic unsaturation and R² is selected from R¹ and alkenyl groups;
(B) at least one organohydrogensilicon compound in an amount sufficient to crosslink (A) selected from
1. (i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H wherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴ is a divalent hydrocarbon group and
2. (ii) an organohydrogensiloxane compound having the formula
  (HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d wherein R¹ and R³ are as defined above,
  1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;
(C) a catalytic amount of a hydrosilylation catalyst; and
optionally (D) an inorganic filler

(II) curing silicone composition (X);

(III) forming a pattern on top of the product of step (II);

(IV) applying a silicone composition (Y) over the pattern of step (III) wherein silicone composition (Y) is obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units and R²₃SiO_1/2 units is from 0 to 15,000 and
(ii) an organosiloxane compound comprising R²3SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0 wherein R² is selected from hydrocarbon groups free of aliphatic unsaturation and alkenyl groups;

(B') at least one organohydrogensilicon compound in an amount sufficient to crosslink (A') selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H and

(ii) an organohydrogensiloxane compound having the formula
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d

wherein R¹ and R³ are each independently a hydrocarbon group free of aliphatic unsaturation, R⁴ is a divalent hydrocarbon group, 1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(C') a catalytic amount of a hydrosilylation catalyst; and optionally (D') an inorganic filler;

(V) curing silicone composition (Y)
with the proviso that the molar ratio of R²₂SiO_2/2 units to all other units combined is higher in silicone composition (X) than in the silicone composition (Y), and the surface energy of the cured composition (X) is lower than the cured silicone composition (Y); and (VI) separating the cured silicone composition (Y) of step (V) from the substrate.

[0027] The ability to reverse the process derives from the minimized composition differences between the two silicone compositions, and the wide range of mechanical properties attainable with these compositions. For most compositions, the only requirement for them to function properly is the higher R²₂SiO_2/2 units in one composition versus the other so that the surface energy of one of the cured compositions is lower than the other.

[0028] The process can also be repeated as follows to build three-dimensional embedded structures. Thus this invention also relates to a method of making an article of manufacture comprising the steps of: (I) applying silicone composition (Y) to a substrate to form a coating 1 to 500 micrometer thick; (II) curing the silicone composition of step (I); (III) forming a pattern on top of the product of step (II); (IV) placing a layer with pattern embedded in on top of the layer, in alignment with but not in contact with the substrate; (V) applying silicone composition (X) onto the surface of the substrate or onto the surface of the layer through capillary flow; (VI) curing silicone composition (X); and (VII) separating the cured silicone composition (X) of step (VI) from the substrate. Silicone compositions (X) and (Y), the curing of the silicone compositions, the method of applying the silicone compositions, and the substrate are all as defined above.

DRAWINGS

[0029]

Figure 1 is an optical microscope image of a carbon black ink pattern printed on the PET film coated with the mixture specified in Example 1.

Figure 2 is an optical microscope image of the printed pattern, shown in Figure 1, embedded into cured Silicone Composition B.

Figure 3 is an SEM image of a carbon black ink pattern printed on the PET film, size of the dots approximately 5 µm in diameter.

Figure 4 is an SEM image of the surface of the cured Silicone Composition A after separation from the printed pattern, at the exact location as in Figure 3.

Figure 5 is an image of the embedded pattern into cured Silicone Composition B.

Figure 6 is an optical microscope image of the cross-section of the embedded pattern in cured Silicone Composition B.

Figure 7 is an SEM image of the cross-section of the embedded pattern in cured Silicone Composition B.

EXAMPLES

[0030] A VCA 2500 goniometer was used to measure water contact angle and surface energies. Water and methylene iodide contact angles were measured by dropping three drops of each liquid on the samples and measuring the tangent angle to the coating. The averages and standard deviations were obtained. The dispersive and polar surface energies were calculated through a geometric mean model.

Example 1

[0031] A PET transparent film was coated by silicone composition (hereinafter denoted Silicone Composition A) containing 24 parts by weight of an organosiloxane compound comprising Me₃SiO_1/2 units, ViMe₂SiO_1/2 units, and SiO₂ units, where Vi denotes vinyl and Me denotes methyl, in a molar ratio of about 0.07 moles of Me₃SiO_1/2 + ViMe₂SiO_1/2 units per mole of SiO₂ units and where the organosiloxane compound contains from 1.75 to 2.3 weight percent of vinyl and 76 parts by weight of a liquid silicone rubber composition containing a mixture of 88 parts by weight of an organosiloxane compound comprising (ViMe₂SiO_1/2)₂ (Me₃SiO_1/2)₁₅ (Me₂SiO_2/2)₈₁ (SiO₂)₂₂ units and 6 parts by weight of an organohydrogensiloxane compound having the formula Me₃SiO(Me₂SiO)₃(MeHSiO)₅SiMe₃. The coating was applied by hand operated roll coater with a blade. The pressure applied on the blade controlled the thickness of the coating and the pressure was adjusted so that a 2 micrometer thick coating was obtained. The coating was cured at 125°C for two hours and cooled to room temperature before use. This coating altered the surface energy of the PET film from 29.2 to 14.0 dyne/cm, as seen in Table 1.

[0032] A carbon black ink dot pattern was printed onto the coated PET film by a laser printer, as shown in Figure 1, an optical microscope image of the pattern on the coated PET film. In the image the dots were approximately 20 micrometers in diameter. Teflon bars one inch tall were glued onto four sides around the printed pattern by a silicone sealant to form a mold with the top open to the air. The mold was left at room temperature and heated at 80°C overnight to cure the silicone sealant.

[0033] A silicone composition (hereinafter denoted Silicone Composition B) was prepared by mixing an organosiloxane compound comprising the units (PhSiO_3/2)_0.75 and (ViMe₂SiO_1/2)_0.25 with an organosiloxane compound having the formula HMe₂Si-Ph-SiMe₂H so the SiH/SiVi ratio was 1.1/1. To this mixture was then added a catalyst containing a platinum-(1-ethynyl cyclohenxan-1-ol)-tetramethyl divinyl disiloxane complex dissolved in toluene at a platinum concentration of 1000 ppm. The catalyst was added at a weight ratio of 0.5 parts of catalyst per 100 parts of the above mixture. The Silicone Composition B was then poured onto the top of the printed pattern encircled by Teflon bars, and left at room temperature overnight to cure. The mold with Silicone Composition B coated thereon was then heated at 60°C for 2 hours to complete the cure. The cured silicone composition had a surface energy of 22 dynes/cm.

[0034] After cure, the mold was cooled to room temperature and the plaque containing cured Silicone Composition B as a top layer and Silicone Composition A as a bottom layer was peeled off from the mold. As seen in Figure 2, the printed pattern cleanly transferred to the silicone plaque from the surface of the coated PET film.

Example 2

[0035] Example 1 was repeated except that the coating thickness of Composition A on the PET film was increased from 2 micrometers to approximately 20 micrometers. As seen the surface energy was altered from 29.2 to 15.5 dynes/cm, by this thicker coating. The same subsequent procedures as described in Example 1 were followed and a clean transfer of the printed pattern was also observed.

Comparison Example 1

[0036] On an un-coated PET transparent film a carbon black ink dot pattern was printed by a laser printer, as shown in Figure 3. A mold was made so that the pattern encircled by Teflon bars, similar to the mold used in Example 1, and the mold was cured similarly. Silicone Composition A was poured onto the surface of the pattern in the mold. Silicone Composition A was then cured at 60°C for 2 hours. Silicone Composition A had a surface energy lower than the PET substrate. After cure the mold was cooled to room temperature and the cured Silicone Composition A was peeled off from the mold. The surface topographic features of the printed pattern were completely and cleanly replicated to the bottom surface of the cured Silicone Composition A. No ink transfer was observed. Figure 4 is an optical microscope image of the pattern replicated onto the cured Silicone Composition A surface at exactly the same location as in Figure 3.

Example 3

[0037] Procedures and compositions used were the same as in Example 1 except the composition of the coating applied to the PET transparent film. In this example the coating composition was a mixture of 50 parts by weight of a mixture of 47.25 parts by weight of an organosiloxane compound comprising (ViMe₂SiO_1/2)₄ (Me₃SiO_1/2)₃₉ (SiO₂)₅₇ units and 3.72 parts by weight of an organosiloxane compound comprising (ViMe₂SiO_1/2)₂ (Me₂SiO_2/2)₇₄₀ units and 50 parts by weight of an organosiloxane compound comprising (ViMe₂SiO_1/2)₂ (Me₂SiO_2/2)₁₄₀ units (hereinafter denoted Silicone Composition C). The cured coating altered the surface energy of the PET film from 29.2 to 15.1 dynes/cm. Clean transfer of printed carbon black ink patterns into cured Composition B was also observed with this coating on the PET film.

Example 4

[0038] Instead of using the 50/50 mixture described in Example 4 as the coating, 100 parts by weight of the mixture of 47.25 parts by weight of an organosiloxane compound comprising (ViMe₂SiO_1/2)₄ (Me₃SiO_1/2)₃₉ (SiO₂)₅₇ units and 3.72 parts by weight of an organosiloxane compound comprising (ViMe₂SiO_1/2)₂ (Me₂SiO_2/2)₇₄₀ units (Silicone Composition D) was used as the coating on the transparent PET film. As seen in Table 1, the surface energy of the cured coating was 20.4 dynes/cm, much higher than the mixture of Example 4. This coating was not suitable for the purpose of transferring or embedding the printed pattern into Silicone Composition B.

Example 5

[0039] Composition and procedures were the same as in Example 1. Instead of a carbon black ink dot pattern, carbon black ink patterns identical to a specific design of RFID antenna were printed onto the coated PET film. These patterns were cleanly transferred into cured Silicone Composition B, Figure 5.

[0040] A close examination of the cross-section of the embedded pattern showed that the pattern was transferred into the silicone composition by controlled release from the interface between the ink pattern and the coated PET. In Figure 6, an optical microscope image of the cross-section of the embedded pattern, the ink pattern was seen to reside on the surface of Silicone Composition B. This was also confirmed by SEM. Silicone Composition B with the pattern was in turn embedded in an epoxy resin and cured. A cross-section was microtomed and observed under SEM. It again showed the location of the ink patterns was on the surface of the silicone composition as shown in Figure 7.

Table 1

Surface Energy of the PET Substrate With and Without Coatings
Example	Coating on PET	Dispersive (dynes/cm)	Polar (dynes/cm)	Total (dynes/cm)
1	Silicone Composition A	13.7	0.3	14.0
2	Silicone Composition A	14.9	0.6	15.5
3	Silicone Composition C	12.6	2.5	15.1
4	Silicone Composition D	20.2	0.2	20.4
Comparison Example 1	None	27.3	1.9	29.2

Claims

1. A silicone coating composition comprising:

(I) a first coating layer comprising a silicone composition (X) obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0,

(ii) an organosiloxane compound comprising R²₃SiO_1/2, units and R¹SiO_3/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹ SiO_3/2 units is from 0.05 to 3.0,

(iii) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹ SiO_3/2 units, and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹ SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 and R¹SiO_3/2 units combined to SiO_4/2 units is from 4 to 99,

(iv) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and R²₂SiO_2/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 units and R¹ SiO_3/2 units combined to R²₂SiO_2/2 units is from 0.5 to 99,

(v) an organosiloxane compound comprising R²₂SiO_2/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R¹SiO_3/2 units is from 0.2 to 4.0,

(vi) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R²₃SiO_1/2 units is from 0 to 15,000, and

(vii) an organosiloxane compound comprising R²₂SiO_2/2 units,
R²₃SiO_1/2 units, and SiO_2/2 units, wherein the molar ratio of SiO_2/2 units to R²₂SiO_2/2 units and R²₃SiO_1/2 units combined is from 0.005 to 0.125
wherein R¹ is a hydrocarbon group free of aliphatic unsaturation and R² is selected from R¹ and alkenyl groups;

(B) at least one organohydrogensilicon compound in an amount sufficient to crosslink (A) selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H wherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴ is a divalent hydrocarbon group and

(ii) an organohydrogensiloxane compound having the formula QXR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d wherein R¹ and R³ are as defined above,
1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(II) a second coating layer in contact with the coating layer (I), the second coating layer comprising a silicone composition (Y) obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units and R²₃SiO_1/2 units is from 0 to 15,000 and

(ii) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0 wherein R² is selected from hydrocarbon groups free of aliphatic unsaturation and alkenyl groups;

(B') at least one organohydrogensilicon compound in an amount sufficient to crosslink (A') selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H and

(ii) an organohydrogensiloxane compound having the formula W_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d
wherein R¹ and R³ are each independently a hydrocarbon group free of aliphatic unsaturation, R⁴ is a divalent hydrocarbon group, 1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(C') a catalytic amount of a hydrosilylation catalyst; and
optionally (D') an inorganic filler
with the proviso that the molar ratio of R²₂SiO_2/2 units to all other units combined is higher in composition (Y) than in composition (X), and the surface energy of composition (Y) is lower than Composition (X).

2. A silicone coating composition according to Claim 1, wherein the hydrocarbon group free of aliphatic unsaturation is independently selected from methyl and phenyl and the alkenyl group is vinyl.

3. A silicone coating composition according to Claim 1, wherein:

(A) is an organosiloxane compound comprising ViMe₂SiO_1/2 units and PhSiO_3/2 units, where the molar ratio of ViMe₂SiO_1/2 units to PhSiO_3/2 is from 0.05 to 3.0;

(B) is an organohydrogensilane compound having the formula HMe₂Si-Ph-SiMe₂H;

(A') is an organosiloxane compound comprising (ViMe₂SiO_1/2) units, (Me₃SiO_1/2) units, (Me₂SiO_2/2) units, and (SiO₂) units wherein the ratio of (ViMe₂SiO_1/2) units + (Me₃SiO_1/2) units to (Me₂SiO_2/2) units is from 1/10000 to 1/5 and the ratio of (Me₂SiO_2/2) units to (SiO₂) units is from 200/1 to 1/4;

(B') is an organohydrogensiloxane compound having the formula Me₃SiO(Me₂SiO)_x(MeHSiO)_ySiMe₃ wherein the value of x+y provides a molecular weight of 134 to 75,000 and there are at least two SiH groups per molecule;

(D) and (D') are selected from hollow microsperes, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, ground quartz, calcium carbonate, magnesium carbonate, diatomaceous earth, wollastonite, calcined clay, clay, talc, kaolin, titanium oxide, bentonite, ferric oxide, zinc oxide, glass balloon, glass beads, mica, glass powder, glass balloons, coal dust, acrylic resin powder, phenolic resin powder, ceramic powder, zeolite, slate powder, organic fibers, and inorganic fibers.

4. A method of making an article of manufacture comprising the steps of:

(I) applying a silicone composition (Y) to a substrate to form a coating 1 to 500 micrometer thick wherein silicone composition (Y) is obtained by a method comprising reacting:

(A') 100 parts by weight of at least one organosiloxane compound containing an average of greater than two alkenyl groups per molecule and having less than 1.5 mol % of silicon-bonded hydroxy groups, wherein the organosiloxane compound is selected from (i) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units and R²₃SiO_1/2 units is between 0 and 15,000 and

(B') at least one organohydrogensilicon compound in an amount sufficient to crosslink (A') selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H and

(ii) an organohydrogensiloxane compound having the formula
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d
wherein R¹ and R³ are each independently a hydrocarbon group free of aliphatic unsaturation, R⁴ is a divalent hydrocarbon group, 1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(C') a catalytic amount of a hydrosilylation catalyst; and
optionally (D') an inorganic filler;

(II) curing silicone composition (Y);

(III) forming a pattern on top of the product of step (II);

(IV) applying a silicone composition (X) over the pattern of step (III) wherein
silicone composition (X) is obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0,

(ii) an organosiloxane compound comprising R²₃SiO_1/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0,

(iii) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 and R¹ SiO_3/2 units combined to SiO_4/2 units is from 4 to 99,

(iv) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and R²₂SiO_2/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 units and R¹SiO_3/2 units combined to R²₂SiO_2/2 units is from 0.5 to 99,

(v) an organosiloxane compound comprising R²₂SiO_2/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R¹SiO_3/2 units is from 0.2 to 4.0,

(vi) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R²3SiO_1/2 units is from 0 to 15,000, and

(vii) an organosiloxane compound comprising R²₂SiO_2/2 units,

R²₃SiO_1/2 units, and SiO_2/2 units, wherein the molar ratio of SiO_2/2 units to R²₂SiO_2/2 units and R²₃SiO_1/2 units combined is from 0.005 to 0.125
wherein R¹ is a hydrocarbon group free of aliphatic unsaturation and R² is selected from R¹ and alkenyl groups;

(B) at least one organohydrogensilicon compound in an amount sufficient to crosslink (A) selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H

wherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴ is a divalent hydrocarbon group and

(ii) an organohydrogensiloxane compound having the formula CHR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d wherein R¹ and R³ are as defined above,

1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

optionally (D) an inorganic filler;

(V) curing silicone composition (X)
with the proviso that the molar ratio of R²₂SiO_2/2 units to all other units combined is higher in silicone composition (Y) than in the silicone composition (X), and the surface energy of the cured composition (Y) is lower than the cured silicone composition (X); and

(VI) separating the cured silicone composition (X) of step (V) from the substrate.

5. A method according to Claim 4, wherein the hydrocarbon group free of aliphatic unsaturation is independently selected from methyl and phenyl and the alkenyl group is vinyl.

6. A method according to Claim 4, wherein:

(A) is an organosiloxane compound comprising ViMe₂SiO_1/2 units and PhSiO_3/2 units, where the molar ratio of ViMe₂SiO_1/2 units to PhSiO_3/2 is from 0.05 to 3.0;

(B) is an organohydrogensilane compound having the formula HMe₂Si-Ph-SiMe₂H;

(A') is an organosiloxane compound comprising (ViMe₂SiO_1/2) units, (Me₃SiO_1/2) units, (Me₂SiO_2/2) units, and (SiO₂) units wherein the ratio of (ViMe₂SiO_1/2) units + (Me₃SiO_1/2) units to (Me₂SiO_2/2) units is from 1/10000 to 1/5 and the ratio of(Me₂SiO_2/2) units to (SiO₂) units is from 200/1 to 1/4;

7. A method of making an article of manufacture comprising the steps of:

(I) applying a silicone composition (X) to a substrate to form a coating 1 to 500 micrometer thick wherein silicone composition (X) is obtained by a method comprising reacting:

(A) 100 parts by weight of at least one organosiloxane compound containing an average of greater than two alkenyl groups per molecule and having less than 1.5 mol % of silicon-bonded hydroxy groups wherein the organosiloxane compound is selected from (i) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0,

(ii) an organosiloxane compound comprising R²₃SiO_1/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0,

(iii) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹ SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 and R¹SiO_3/2 units combined to SiO_4/2 units is from 4 to 99,

(iv) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and R²₂SiO_2/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 units and R¹SiO_3/2 units combined to R²₂SiO_2/2 units is from 0.5 to 99,

(v) an organosiloxane compound comprising R²₂SiO_2/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R¹SiO_3/2 units is from 0.2 to 4.0, and

(vi) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R²₃SiO_1/2 units is from 0 to 15,000
wherein R¹ is a hydrocarbon group free of aliphatic unsaturation and R² is selected from R¹ and alkenyl groups;

(B) at least one organohydrogensilicon compound in an amount sufficient to crosslink (A) selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H wherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴ is a divalent hydrocarbon group and

(ii) an organohydrogensiloxane compound having the formula
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d wherein R1 and R3 are as defined above,
1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(II) curing silicone composition (X);

(III) forming a pattern on top of the product of step (II);

(IV) applying a silicone composition (Y) over the pattern of step (III) wherein silicone composition (Y) is obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units and R²₃SiO_1/2 units is from 0 to 15,000 and

(B') at least one organohydrogensilicon compound in an amount sufficient to crosslink (A') selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H and

(C') a catalytic amount of a hydrosilylation catalyst; and
optionally (D') an inorganic filler;

(VI) separating the cured silicone composition (Y) of step (V) from the substrate.

8. A method according to Claim 7, wherein the hydrocarbon group free of aliphatic unsaturation is independently selected from methyl and phenyl and the alkenyl group is vinyl.

9. A method according to Claim 7, wherein:

(A) is an organosiloxane compound comprising ViMe₂SiO_1/2 units and PhSiO_3/2 units, where the molar ratio of ViMe₂SiO_1/2 units to PhSiO_3/2 is from 0.05 to 3.0;

(B) is an organohydrogensilane compound having the formula HMe₂Si-Ph-SiMe₂H;

(A') is an organosiloxane compound comprising (ViMe₂SiO_1/2) units, (Me₃SiO_1/2) units, (Me₂SiO_2/2) units, and (SiO₂) units wherein the ratio of (ViMe₂SiO_1/2) units + (Me₃SiO_1/2) units, to (Me₂SiO_2/2) units, is from 1/10000 to 1/5 and the ratio of (Me₂SiO_2/2) units to (SiO₂) units is from 200/1 to 1/4;

10. A method of making an article of manufacture comprising the steps of:

(I) applying a silicone composition (Y) to a substrate to form a coating 1 to 500 micrometer thick wherein silicone composition (Y) is obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₂SiO_2/2 units and R²₃SiO_1/2 units, wherein the molar ratio of R²₂SiO_2/2 units and R²₃SiO_1/2 units is from 0 to 15,000 and

(B') at least one organohydrogensilicon compound in an amount sufficient to crosslink (A') selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H and

(ii) an organohydrogensiloxane compound having the formula
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d
wherein R¹ and R³ are each independently a hydrocarbon group free of aliphatic unsaturation, R⁴ is a divalent hydrocarbon group, 1 ≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(C') a catalytic amount of a hydrosilylation catalyst; and
optionally (D') an inorganic filler;

(II) curing silicone composition (Y);

(III) forming a pattern on top of the product of step (II);

(IV) placing a layer with the pattern embedded in on top of the layer, in alignment with but not in contact with the substrate;

(V) applying a silicone composition (X) onto the surface of the substrate or onto the surface of the layer through capillary flow wherein silicone composition (X) is obtained by a method comprising reacting:

(i) an organosiloxane compound comprising R²₃SiO_1/2 units and SiO_4/2 units, wherein the molar ratio of R²₃SiO_1/2 units to SiO_4/2 units is from 0.05 to 4.0,

(ii) an organosiloxane compound comprising R²₃SiO_1/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0,

(iii) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and SiO_4/2 units, wherein the molar ratio ofR²₃SiO_1/2 units to R¹SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 and R¹SiO_3/2 units combined to SiO_4/2 units is from 4 to 99,

(iv) an organosiloxane compound comprising R²₃SiO_1/2 units, R¹SiO_3/2 units, and R²2SiO_2/2 units, wherein the molar ratio of R²₃SiO_1/2 units to R¹ SiO_3/2 units is from 0.05 to 3.0, and the molar ratio of R²₃SiO_1/2 units and R¹SiO_3/2 units combined to R²₂SiO_2/2 units is from 0.5 to 99,

(v) an organosiloxane compound comprising R²₂SiO_2/2 units and R¹SiO_3/2 units, wherein the molar ratio of R²₂SiO_2/2 units to R¹SiO_3/2 units is from 0.2 to 4.0, and

(B) at least one organohydrogensilicon compound in an amount sufficient to crosslink (A) selected from

(i) an organohydrogensilane compound having the formula HR³₂SiR⁴SiR³₂H wherein R³ is a hydrocarbon group free of aliphatic unsaturation and R⁴ is a divalent hydrocarbon group and

(ii) an organohydrogensiloxane compound having the formula
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d wherein R¹ and R³ are as defined above,
1≤ a ≤2, 0≤ c ≤3, the value of b+d provides a molecular weight of 134 to 75,000, and with the proviso that there are at least two SiH groups per molecule;

(VI) curing silicone composition (X)
with the proviso that the molar ratio of R²₂SiO_2/2 units to all other units combined is higher in silicone composition (Y) than in the silicone composition (X), and the surface energy of the cured composition (Y) is lower than the cured silicone composition (X); and

(VII) separating the cured silicone composition (X) of step (VI) from the substrate.

Ansprüche

1. Siliconbeschichtungszusammensetzung umfassend:

(1) eine erste Überzugsschicht, die eine Siliconzusammensetzung (X) enthält, die nach einem Verfahren erhalten wird, das Umsetzen von (A) 100 Gewichtsteilen mindestens einer Organosiloxanverbindung, die durchschnittlich mehr als zwei Alkenylgruppen pro Molekül enthält und weniger als 1,5 mol-% siliciumgebundene Hydroxygruppen aufweist, wobei die Organosiloxanverbindung ausgewählt ist aus

(i) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten und SiO_4/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu SiO_4/2-Einheiten von 0,05 bis 4,0 reicht,

(ii) einer Organosiloxanverbindung, die R²₃siO_1/2-Einheiten und R¹SiO_3/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu R¹SiQ_3/2-Einheiten von 0,05 bis 3,0 reicht,

(iii) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten, R¹SiO_3/2-Einheiten und SiO_4/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu R¹SiO_3/2-Einheiten von 0,05 bis 3,0 reicht und das Molverhältnis von R²₃SiO_1/2-Einheiten und R¹SiO_3/2-Einheiten in Kombination zu SiO_4/2-Einheiten von 4 bis 99 reicht,

(iv) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten, R¹SiO_3/2-Einheiten und R²₂SiO_2/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu R¹SiO_3/2-Einheiten von 0,05 bis 3,0 reicht und das Molverhältnis von R²₃SiO_1/2-Einheiten und R¹SiO_3/2-Einheiten in Kombination zu R²₂SiO_2/2-Einheiten von 0,5 bis 99 reicht,

(v) einer Organosiloxanverbindung, die R²₂SiO_2/2-Einheiten und R¹SiO_3/2-Einheiten enthält, wobei das Molverhältnis von R²₂SiO_2/2-Einheiten zu R¹SiO_3/2-Eirxheiten von 0,2 bis 4,0 reicht,

(vii) einer Organosiloxanverbindung, die R²₂SiO_2/2-Einheiten, R²₃SiO_1/2-Einheiten und SiO_2/2-Einheiten enthält, wobei das Molverhältnis von SiO_2/2-Einheiten zu R²₂SiO_2/2-Einheiten und R²₃SiO_1/2-Einheiten in Kombination von 0,005 bis 0,125 reicht,
worin R¹ eine Kohlenwasserstoffgruppe ist, die frei von aliphatischer Ungesättigtheit ist, und R² aus R¹ und Alkenylgruppen ausgewählt ist;

(B) mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A) zu vernetzen, ausgewählt aus

(i) einer Organowasserstoffsilanverbindung mit der Formel HR³₂SiR⁴SiR³₂H, worin R³ eine Kohlenwasserstoffgruppe ist, die frei von aliphatischer Ungesättigtheit ist, und R⁴ eine divalente Kohlenwasserstoffgruppe ist, und

(ii) einer Organowasserstoffsiloxanverbindung mit der Formel
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d, worin R¹ und R³ wie oben definiert sind, 1 ≤ a ≤ 2, 0 ≤ c ≤ 3, der Wert von b + d ein Molekulargewicht von 134 bis 75.000 gewährleistet und unter der Voraussetzung, dass mindestens zwei SiH-Gruppen pro Molekül vorhanden sind;

(C) einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D) einem anorganischen Füllstoff umfasst, und

(II) eine zweite Überzugsschicht, in Kontakt mit der Überzugsschicht (I), wobei die zweite Überzugsschicht eine Siliconzusammensetzung (Y) enthält, die nach einem Verfahren erhalten wird, das Umsetzen von (A') 100 Gewichtsteilen mindestens einer Organosiloxanverbindung, die durchschnittlich mehr als zwei Alkenylgruppen pro Molekül enthält und weniger als 1,5 mol-% siliciumgebundene Hydroxygruppen aufweist, wobei die Organosiloxanverbindung ausgewählt ist aus

(i) einer Organosiloxanverbindung, die R²₂SiO_2/2-Einheiten und R²₃SiO_1/2-Einheiten enthält, wobei das Molverhältnis von R²₂SiO_2/2-Einheiten zu R²₃SiO_1/2-Einheiten von 0 bis 15.000 reicht,

(ii) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten und SiO_4/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu SiO_4/2-Einheiten von 0,05 bis 4,0 reicht,
worin R² aus Kohlenwasserstoffgruppen, die frei von aliphatischer Ungesättigtheit sind und Alkenylgruppen ausgewählt ist;

(B') mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A') zu vernetzen, ausgewählt aus

(i) einer Organowasserstoffsilanverbindung mit der Formel HR³₂SiR⁴SiR³₂H und

(ii) einer Organowasserstoffsiloxanverbindung mit der Formel
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d
worin R¹ und R³ jeweils unabhängig voneinander eine Kohlenwasserstoffgruppe sind, die frei von aliphatischer Ungesättigtheit ist, R⁴ eine divalente Kohlenwasserstoffgruppe ist, 1 ≤ a ≤ 2, 0 ≤ c ≤ 3, der Wert von b + d ein Molekulargewicht von 134 bis 75.000 gewährleistet und unter der Voraussetzung, dass mindestens zwei SiH-Gruppen pro Molekül vorhanden sind;

(C') einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D') einem anorganischen Füllstoff umfasst,
unter der Voraussetzung, dass das Molverhältnis von R²₂SiO_2/2-Einheiten zu allen anderen Einheiten in Kombination in Zusammensetzung (Y) größer ist als in Zusammensetzung (X) und die Oberflächenenergie der Zusammensetzung (Y) niedriger ist als die der Zusammensetzung (X).

2. Siliconbeschichtungszusammensetzung gemäß Anspruch 1, wobei die Kohlenwasserstoffgruppe, die frei von aliphatischer Ungesättigtheit ist, unabhängig voneinander aus Methyl und Phenyl ausgewählt ist und die Alkenylgruppe Vinyl ist.

3. Siliconbeschichtungszusammensefizung gemäß Anspruch 1, wobei

(A) eine Organosiloxanverbindung ist, die ViMe₂SiO_1/2-Einheiten und PhSiO_3/2-Einheiten enthält, wobei das Molverhältnis von ViMe₂SiO_1/2-Einheiten zu PhSiO_3/2-Einheiten von 0,05 bis 3,0 reicht;

(B) eine Organowasserstoffsilanverbindung mit der Formel HMe₂Si-Ph-SiMe₂H ist;

(A') eine Organosiloxanverbindung ist, die ViMe₂SiO_1/2-Einheiten, Me₃SiO_1/2-Einheiten, Me₂SiO_2/2-Einheiten und SiO₂-Einheiten enthält, wobei das Verhältnis von ViMe₂SiO_1/2-Einheiten + Me₃SiO_1/2-Einheiten zu Me₂SiO_2/2-Einheiten von 1/10.000 bis 1/5 reicht und das Verhältnis von Me₂SiO_2/2-Einheiten zu SiO₂-Einheiten von 200/1 bis 1/4 reicht;

(B') eine Organowasserstoffsiloxanverbindung mit der Formel Me₃SiO(Me₂SiO)_x(MeHSiO)_ySiMe₃ ist, wobei der Wert von x + y ein Molekulargewicht von 134 bis 75.000 gewährleistet und wobei mindestens zwei SiH-Gruppen pro Molekül vorhanden sind;

(D) und (D') ausgewählt sind aus hohlen Mikrokügelchen, pyrogener Kieselsäure, Fällungskieselsäure, Kieselsäureanhydrid, wasserhaltiger Kieselsäure, Ruß, gemahlenem Quarz, Calciumcarbonat, Magnesiumcarbonat, Diatomeenerde, Wollastonit, calciniertem Ton, Ton, Talk, Kaolin, Titanoxid, Bentonit, Eisen(III)-oxid, Zinkoxid, Glasballons, Glasperlen, Glimmer, Glaspulver, Kohlestaub, Acrylharzpulver, Phenolharzpulver, keramischem Pulver, Zeolith, Schieferpulver, organischen Fasern und anorganischen Fasern.

4. Verfahren zur Herstellung eines Erzeugnisses, umfassend die Schritte:

(I) Aufbringen einer Siliconzusammensetzung (Y) auf ein Substrat, um eine 1 bis 500 µm dicke Beschichtung zu bilden, wobei die Siliconzusammensetzung (Y) nach einem Verfahren erhalten wird, das Umsetzen von

(A') 100 Gewichtsteilen mindestens einer Organosiloxanverbindung, die durchschnittlich mehr als zwei Alkenylgruppen pro Molekül enthält und weniger als 1,5 mol-% siliciumgebundene Hydroxygruppen aufweist, wobei die Organosiloxanverbindung ausgewählt ist aus

(B') mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A') zu vernetzen, ausgewählt aus

(i) einer Organowasserstoffsilanverbindung mit der Formel HR³₂SiR⁴SiR³₂H und

(ii) einer Organowasserstoffsiloxanverbindung mit der Formel
(HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d,
worin R¹ und R³ jeweils unabhängig voneinander eine Kohlenwasserstoffgruppe sind, die frei von aliphatischer Ungesättigtheit ist, R⁴ eine divalente Kohlenwasserstoffgruppe ist, 1 ≤ a ≤ 2, 0 ≤ c ≤ 3, der Wert von b + d ein Molekulargewicht von 134 bis 75.000 gewährleistet und unter der Voraussetzung, dass mindestens zwei SiH-Gruppen pro Molekül vorhanden sind;

(C') einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D') einem anorganischen Füllstoff umfasst;

(II) Härten der Siliconzusammensetzung (Y);

(III) Ausbilden eines Musters auf dem Produkt von Schritt (II);

(IV) Aufbringen einer Siliconzusammensetzung (X) über das Muster aus Schritt (III), wobei die Siliconzusammensetzung (X) nach einem Verfahren erhalten wird, das Umsetzen von

(A) 100 Gewichtsteilen mindestens einer Organosiloxanverbindung, die durchschnittlich mehr als zwei Alkenylgruppen pro Molekül enthält und weniger als 1,5 mol-% siliciumgebundene Hydroxygruppen aufweist, wobei die Organosiloxanverbindung ausgewählt ist aus

(i) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten und SiO_4/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu SiO_4/2-Einheiten von 0,05 bis 4,0 reicht,

(ii) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten und R¹SiO_3/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu R¹SiO_3/2-Einheiten von 0,05 bis 3,0 reicht,

(v) einer Organosiloxanverbindung, die R²₂SiO_2/2-Einheiten und R¹SiO_3/2-Einheiten enthält, wobei das Molverhältnis von R²₂SiO_2/2-Einheiten zu R¹SiO_3/2-Einheiten von 0,2 bis 4,0 reicht,

(B) mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A) zu vernetzen, ausgewählt aus

(C) einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D) einem anorganischen Füllstoff umfasst;

(V) Härten der Siliconzusammensetzung (X),
unter der Voraussetzung, dass das Molverhältnis von R²₂SiO_2/2-Einheiten zu allen anderen Einheiten in Kombination in der Siliconzusammensetzung (Y) größer ist als in der Siliconzusammensetzung (X) und die Oberflächenenergie der gehärteten Zusammensetzung (Y) niedriger ist als die der gehärteten Siliconzusammensetzung (X), und (VI) Trennen der gehärteten Siliconzusammensetzung (X) aus Schritt (V) von dem Substrat.

5. Verfahren gemäß Anspruch 4, wobei die Kohlenwasserstoffgruppe, die frei von aliphatischer Ungesättigtheit ist, unabhängig voneinander aus Methyl und Phenyl ausgewählt ist und die Alkenylgruppe Vinyl ist.

6. Verfahren gemäß Anspruch 4, wobei

(B) eine Organowasserstoffsilanverbindung mit der Formel HMe₂Si-Ph-SiMe₂H ist;

7. Verfahren zur Herstellung eines Erzeugnisses, umfassend die Schritte:

(I) Aufbringen einer Siliconzusammensetzung (X) auf einem Substrat, um eine 1 bis 500 µm dicke Beschichtung zu bilden, wobei die Siliconzusammensetzung (X) nach einem Verfahren erhalten wird, das Umsetzen von

(A) 100 Gewichtsteilen einer Organosiloxanverbindung, die durchschnittlich mehr als zwei Alkenylgruppen pro Molekül enthält und weniger als 1,5 mol-% siliciumgebundene Hydroxygruppen aufweist, wobei die Organosiloxanverbindung ausgewählt ist aus

(i) einer Grganasüoxanverbindung, die R²₃SiO_1/2-Einheiten und SiO_4/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu SiO_4/2-Einheiten von 0,05 bis 4,0 reicht,

(v) einer Organosiloxanverbindung, die R²₂SiO_2/2-Einheiten und R¹SiO_3/2-Einheiten enthält, wobei das Molverhältnis von R²₂SiO_2/2-Einheiten zu R¹SiO_3/2-Einheiten von 0,2 bis 4,0 reicht und

(vi) einer Organosiloxanverbindung, die R²₂SiO_2/2-Einheiten und R²₃SiO_1/2-Einheiten enthält, wobei das Molverhältnis von R²₂SiO_2/2-Einheiten zu R²₃SiO_1/2-Einheiten von 0 bis 15.000 reicht,
worin R¹ eine Kohlenwasserstoffgruppe ist, die frei von aliphatischer Ungesättigtheit ist, und R² aus R¹ und Alkenylgruppen ausgewählt ist;

(B) mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A) zu vernetzen, ausgewählt aus

(II) Härten der Siliconzusammensetzung (X);

(III) Ausbilden eines Musters auf dem Produkt aus Schritt (II);

(IV) Aufbringen einer Siliconzusammensetzung (Y) über das Muster aus Schritt (III), wobei die Siliconzusammensetzung (Y) nach einem Verfahren erhalten wird, das Umsetzen von

(B') mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A') zu vernetzen, ausgewählt aus

(i) einer Organowasserstoffsilanverbindung mit der Formel HR³₂SiR⁴SiR³₂H und

(C') einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D') einem anorganischen Füllstoff umfasst;

(V) Härten der Siliconzusammensetzung (Y),
unter der Voraussetzung, dass das Molverhältnis von R²₂SiO_2/2-Einheiten zu allen anderen Einheiten in Kombination in der Siliconzusammensetzung (X) größer ist als in der Siliconzusammensetzung (Y) und die Oberflächenenergie der gehärteten Zusammensetzung (X) niedriger ist als die der gehärteten Siliconzusammensetzung (Y), und (VI) Trennen der gehärteten Siliconzusammensetzung (Y) aus Schritt (V) von dem Substrat.

8. Verfahren gemäß Anspruch 7, wobei die Kohlenwasserstoffgruppe, die frei von aliphatischer Ungesättigtheit ist, unabhängig voneinander aus Methyl und Phenyl ausgewählt ist und die Alkenylgruppe Vinyl ist.

9. Verfahren gemäß Anspruch 7, wobei

(B) eine Organowasserstoffsilanverbindung mit der Formel HMe₂Si-Ph-SiMe₂H ist;

10. Verfahren zur Herstellung eines Erzeugnisses, umfassend die Schritte:

(B') mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A') zu vernetzen, ausgewählt aus

(i) einer Organowasserstoffsilanverbindung mit der Formel HR³₂SiR⁴SiR³₂H und

(C') einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D') einem anorganischen Füllstoff umfasst;

(II) Härten der Siliconzusammensetzung (Y);

(III) Ausbilden eines Musters auf dem Produkt aus Schritt (II);

(IV) Anordnen einer Schicht mit dem Muster darin eingebettet auf der Schicht, in Ausrichtung aber nicht in Kontakt mit dem Substrat;

(V) Aufbringen einer Siliconzusammensetzung (X) auf die Oberfläche des Substrats oder auf die Oberfläche der Schicht durch Kapillarfluss, wobei die Siliconzusammensetzung (X) nach einem Verfahren erhalten wird, das Umsetzen von

(i) einer Organosiloxanverbindung, die R²₃SiO_1/2-Einheiten und SiO_4/2-Einheiten enthält, wobei das Molverhältnis von R²₃SiO_1/2-Einheiten zu SiO_4/2-Einheiten von 0,05 bis 4,0 reicht,

(B) mindestens einer Organowasserstoffsiliciumverbindung in einer Menge, die ausreichend ist, um (A) zu vernetzen, ausgewählt aus

(C) einer katalytischen Menge eines Hydrosilylierungskatalysators
und
optional (D) einem anorganischen Füllstoff umfasst;

(VI) Härten der Siliconzusammensetzung (X),
unter der Voraussetzung, dass das Molverhältnis von R²₂SiO_2/2-Einheiten zu allen anderen Einheiten in Kombination in der Siliconzusammensetzung (Y) größer ist als in der Siliconzusammensetzung (X) und die Oberflächenenergie der gehärteten Zusammensetzung (Y) niedriger ist als die der gehärteten Zusammensetzung (X), und

(VII) Trennen der gehärteten Siliconzusammensetzung (X) aus Schritt (VI) von dem Substrat.

Revendications

1. Composition de revêtement de silicone comprenant :

(I) une première couche de revêtement comprenant une composition de silicone (X) obtenue par un procédé comprenant la réaction :

(A) de 100 parties en poids d'au moins un composé organosiloxane contenant une moyenne de plus de deux groupes alcényle par molécule et comportant moins de 1,5 % en mole de groupes hydroxy liés à du silicium où le composé organosiloxane est choisi parmi

(i) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs SiO_4/2 vaut de 0,05 à 4,0,

(ii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0,

(iii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2, des motifs R¹SiO_3/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0, et le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 combinés et les motifs SiO_4/2 vaut de 4 à 99,

(iv) un composé organosiloxane comprenant des motifs R²₃SiO_1/2, des motifs R¹SiO_3/2 et des motifs R²₂SiO_2/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0, et le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 combinés et les motifs R²₂SiO_2/2 vaut de 0,5 à 99,

(v) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R¹SiO_3/2 vaut de 0,2 à 4,0,

(vii) un composé organosiloxane comprenant des motifs R²₂SiO_2/2, des motifs R²₃SiO_1/2 et des motifs SiO_2/2, où le rapport molaire entre les motifs SiO_2/2 et les motifs R²₂SiO_2/2 et les motifs R²₃SiO_1/2 combinés vaut de 0,005 à 0,125
où R¹ est un groupe hydrocarbure dépourvu d'insaturation aliphatique, et R² est choisi parmi R¹ et les groupes alcényle ;

(B) d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A) choisi parmi

(i) un composé organohydrogénosilane répondant à la formule HR³₂SiR⁴SiR³₂H où R³ est un groupe hydrocarbure dépourvu d'insaturation aliphatique et R⁴ est un groupe hydrocarbure divalent et

(ii) un composé organohydrogénosiloxane répondant à la formule (HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d dans laquelle R¹ et R³ sont tels que définis ci-dessus, 1 ≤ a ≤2, 0 ≤ c ≤3, la valeur de b + d fournit une masse moléculaire de 134 à 75 000, et à condition qu'il y ait au moins deux groupes SiH par molécule ;

(II) une seconde couche de revêtement en contact avec la couche de revêtement (I), la seconde couche de revêtement comprenant une composition de silicone (Y) obtenue par le procédé comprenant la réaction :

(A') de 100 parties en poids d'au moins un composé organosiloxane contenant une moyenne de plus de deux groupes alcényle par molécule et comportant moins de 1,5 % en mole de groupes hydroxy liés à du silicium où le composé organosiloxane est choisi parmi

(i) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R²₃SiO_1/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R²₃SiO_1/2 vaut de 0 à 15 000, et

(ii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs SiO_4/2 vaut de 0,05 à 4,0, où R² est choisi parmi les groupes hydrocarbures dépourvus d'insaturation aliphatique et les groupes alcényle ;

(B') d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A') choisi parmi

(i) un composé organohydrogénosilane répondant à la formule HR³₂SiR⁴SiR³₂H et

(ii) un composé organohydrogénosiloxane répondant à la formule (HR³_aSiO_(3-a)/2)_b(R¹_cSiO_(4-c)/2)_d
où R¹ et R³ sont chacun indépendamment un groupe hydrocarbure dépourvu d'insaturation aliphatique, R⁴ est un groupe hydrocarbure divalent, 1 ≤ a ≤ 2, 0 ≤ c ≤ 3, la valeur de b + d fournit une masse moléculaire de 134 à 75 000, et à condition qu'il y ait au moins deux groupes SiH par molécule ;

(C') d'une quantité catalytique d'un catalyseur d'hydrosilylation ;
facultativement (D) d'une charge inorganique
à condition que le rapport molaire entre les motifs R²₂SiO_2/2 et tous les autres motifs combinés soit plus élevé dans la composition (Y) que dans la composition (X), et que l'énergie de la surface de composition (Y) soit inférieure à celle de la composition (X).

2. Composition de revêtement de silicone selon la revendication 1, dans lequel le groupe hydrocarbure dépourvu d'instauration aliphatique est indépendamment choisi parmi le méthyle et le phényle et le groupe alcényle est un vinyle.

3. Composition de revêtement de silicone selon la revendication 1, dans laquelle :

(A) est un composé organosiloxane comprenant des motifs ViMe₂SiO_1/2 et des motifs PhSiO_3/2, où le rapport molaire entre les motifs ViMe₂SiO_1/2 et les motifs PhSiO_3/2 vaut de 0,05 à 3,0 ;

(B) est un composé organohydrogénosilane répondant à la formule HMe₂Si-Ph-SiMe₂H ;

(A') est un composé organosiloxane comprenant des motifs (ViMe₂SiO_1/2), des motifs (Me₃SiO_1/2), des motifs (Me₂SiO_2/2) et des motifs (SiO₂) où le rapport entre les motifs (ViMe₂SiO_1/2) + les motifs (Me₃SiO_1/2) et les motifs (Me₂SiO_2/2) vaut de 1/10000 à 1/5 et le rapport entre les motifs (Me₂SiO_2/2) et les motifs (SiO₂) vaut de 200/1 à 1/4 ;

(B') est un composé organohydrogénosiloxane répondant à la formule Me₃SiO(Me₂SiO)_x(MeHSiO)_ySiMe₃ dans laquelle la valeur de x + y fournit une masse moléculaire de 134 à 75 000 et il y a au moins deux groupes SiH par molécule ;

(D) et (D') sont choisis parmi les microsphères creuses, la silice fumée, la silice précipitée, l'anhydride silicique, l'acide silicique hydraté, le noir de carbone, le quartz broyé, le carbonate de calcium, le carbonate de magnésium, la terre de diatomée, la wollastonite, l'argile calcinée, l'argile, le talc, le kaolin, l'oxyde de titane, la bentonite, l'oxyde ferrique, l'oxyde de zinc, le ballonnet de verre, les billes de verre, le mica, la poudre de verre, les ballonnets de verre, la poussière de charbon, la poudre de résine acrylique, la poudre de résine phénolique, la poudre céramique, la zéolite, la poudre d'ardoise, les fibres organiques, et les fibres inorganiques.

4. Procédé de production d'un article de manufacture comprenant les étapes consistant à :

(I) appliquer une composition de silicone (Y) à un substrat pour former un revêtement épais de 1 à 500 micromètres dans lequel la composition de silicone (Y) est obtenue par un procédé comprenant la réaction :

(i) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R²₃SiO_1/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R²₃SiO_1/2 est compris entre 0 et 15 000 et

(ii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs SO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs SiO_4/2 vaut de 0,05 à 4,0, où R² est choisi parmi les groupes hydrocarbures dépourvus d'insaturation aliphatique et les groupes alcényle ;

(B') d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A') choisi parmi

(i) un composé organohydrogénosilane répondant à la formule HR³₂SiR⁴SiR³₂H et

(C') d'une quantité catalytique d'un catalyseur d'hydrosilylation ; et facultativement (D') d'une charge inorganique ;

(II) durcir la composition de silicone (Y) ;

(III) former un motif au sommet du produit de l'étape (II) ;

(IV) appliquer une composition de silicone (X) sur le motif de l'étape (III) où la composition de silicone (X) est obtenue par un procédé comprenant la réaction :

(i) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs SiO_4/2 vaut de 0,05 à 4,0,

(ii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0,

(iii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2, des motifs R¹SiO_3/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0, et le rapport molaire entre les motifs R²₃SiO_1/2 et R¹SiO_3/2 combinés et les motifs SiO_4/2 vaut de 4 à 99,

(v) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R¹SiO_3/2 vaut de 0,2 à 4,0,

(B) d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A) choisi parmi

(i) un composé organohydrogénosilane répondant à la formule HR³₂SiR⁴SiR³₂H
où R³ est un groupe hydrocarbure dépourvu d'insaturation aliphatique et R⁴ est un groupe hydrocarbure divalent et

(V) durcir la composition de silicone (X)
à condition que le rapport molaire entre les motifs R²₂SiO_2/2 et tous les autres motifs combinés soit plus élevé dans la composition de silicone (Y) que dans la composition de silicone (X), et que l'énergie de la surface de composition durcie (Y) soit inférieure à celle de la composition de silicone durcie (X) ; et

(VI) séparer la composition de silicone durcie (X) de l'étape (V) du substrat.

5. Procédé selon la revendication 4, dans lequel le groupe hydrocarbure dépourvu d'insaturation aliphatique est indépendamment choisi parmi le méthyle et le phényle et le groupe alcényle est un vinyle.

6. Procédé selon la revendication 4, dans lequel :

(A) est un composé organosiloxane comprenant des motifs ViMe₂SiO_1/2 et des motifs PhSiO_3/2, où le rapport molaire entre les motifs ViMe₂SiO_1/2 et les motifs PhSiO_3/2 vaut de 0,05 à 3,0 ;

(B) est un composé organohydrogénosilane répondant à la formule HMe₂Si-Ph-SiMe₂H ;

(A') est un composé organosiloxane comprenant des motifs (ViMe₂SiO_1/2), des motifs (Me₃SiO_1/2), des motifs (Me₂SiO_2/2) et des motifs (SiO₂) où le rapport entre les motifs (ViMe₂SiO_1/2) + les motifs (Me₃SiO_1/2) et les motifs (Me₂SiO_2/2) vaut de 1/ 10000 à 1/5 et le rapport entre les motifs (Me₂SiO_2/2) et les motifs (SiO₂) vaut de 200/1 à 1/4 ;

(D) et (D') sont choisis parmi les microsphères creuses, la silice fumée, la silice précipitée, l'anhydride silicique, l'acide silicique hydraté, le noir de carbone, le quartz broyé, le carbonate de calcium, le carbonate de magnésium, la terre de diatomée, la wollastonite, l'argile calcinée, l'argile, le talc, le kaolin, l'oxyde de titane, la bentonite, l'oxyde ferrique, l'oxyde de zinc, le ballonnet de verre, les billes de verre, le mica, la poudre de verre, les ballonnets de verre, la poussière de charbon, la poudre de résine acrylique, la poudre de résine phénolique, la poudre céramique, la zéolite , la poudre d'ardoise, les fibres organiques, et les fibres inorganiques.

7. Procédé de production d'un article de manufacture comprenant les étapes consistant à :

(I) appliquer une composition de silicone (X) à un substrat pour former un revêtement épais de 1 à 500 micromètres dans lequel la composition de silicone (X) est obtenue par un procédé comprenant la réaction :

(i) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs SiO_4/2 vaut de 0,05 à 4,0,

(ii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0,

(iii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2, des motifs R¹SiO_3/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0, et le rapport molaire entre les motifs R²₃SiO_1/2 et R¹SiO_3/2 combinés et les motifs SiO_4/2 vaut de 4 à 99,

(v) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R¹SiO_3/2 vaut de 0,2 à 4,0, et

(vi) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R²₃SiO_1/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R²₃SiO_1/2 vaut de 0 à 15 000
où R¹ est un groupe hydrocarbure dépourvu d'insaturation aliphatique et R² est choisi parmi R¹ et les groupes alcényle ;

(B) d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A) choisi parmi

(ii) un composé organohydrogénosiloxane répondant à la formule (HR³_aSiO_(3-a)/2)b(R¹_cSiO_(4-c)/2)_d dans laquelle R¹ et R³ sont tels que définis ci-dessus, 1 ≤ a ≤2, 0 ≤ c ≤3, la valeur de b + d fournit une masse moléculaire de 134 à 75 000, et à condition qu'il y ait au moins deux groupes SiH par molécule ;

(II) durcir la composition de silicone (X) ;

(III) former un motif au sommet du produit de l'étape (II) ;

(IV) appliquer une composition de silicone (Y) sur le motif de l'étape (III) où la composition de silicone (Y) est obtenue par un procédé comprenant la réaction :

(i) un composé organosiloxane comprenant des motifs R²₂SiO_1/2 et des motifs R²₃SiO_1/2, où le rapport molaire entre les motifs R²₂SiO_1/2 et les motifs R²₃SiO_1/2 vaut de 0 à 15 000 et

(B') d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A') choisi parmi

(i) un composé organohydrogénosilane répondant à la formule HR³₂SiR⁴SiR³₂H et

(C') d'une quantité catalytique d'un catalyseur d'hydrosilylation ; et
facultativement (D') d'une charge inorganique ;

(V) durcir la composition de silicone (Y)
à condition que le rapport molaire entre les motifs R²₂SiO_2/2 et tous les autres motifs combinés soit plus élevé dans la composition de silicone (X) que dans la composition de silicone (Y), et que l'énergie de la surface de composition durcie (X) soit inférieure à celle de la composition de silicone durcie (Y) ; et

(VI) séparer la composition de silicone durcie (Y) de l'étape (V) du substrat.

8. Procédé selon la revendication 7, dans lequel le groupe hydrocarbure dépourvu d'insaturation aliphatique est indépendamment choisi parmi le méthyle et le phényle et le groupe alcényle est un vinyle.

9. Procédé selon la revendication 7, dans lequel :

(A) est un composé organosiloxane comprenant des motifs ViMe₂SiO_1/2 et des motifs PhSiO_3/2, où le rapport molaire entre les motifs ViMe₂SiO_1/2 et les motifs PhSiO_3/2 vaut de 0,05 à 3,0 ;

(B) est un composé organohydrogénosilane répondant à la formule HMe₂Si-Ph-SiMe₂H ;

(D) et (D') sont choisis parmi les microsphères creuses, la silice fumée, la silice précipitée, l'anhydride silicique, l'acide silicique hydraté, le noir de carbone, le quartz broyé, le carbonate de calcium, le carbonate de magnésium, la terre de diatomée, la wollastonite, l'argile calcinée, l'argile, le talc, le kaolin, l'oxyde de titane, la bentonite, l'oxyde ferrique, l'oxyde de zinc, le ballonnet de verre, les billes de verre, le mica, la poudre de verre, les ballonnets de verre, la poussière de charbon, la poudre de résine acrylique, la poudre de résine phénolique, la poudre céramique, la zéolite , la poudre d'ardoise, les fibres organiques, et les fibres inorganiques.

10. Procédé de production d'un article de manufacture comprenant les étapes consistant à :

(B') d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A') choisi parmi

(i) un composé organohydrogénosilane répondant à la formule HR³₂SiR⁴SiR³₂H et

(C') d'une quantité catalytique d'un catalyseur d'hydrosilylation ; et
facultativement (D') d'une charge inorganique ;

(II) durcir la composition de silicone (Y) ;

(III) former un motif au sommet du produit de l'étape (II) ;

(IV) placer une couche au sommet de laquelle est incorporé le motif, en alignement mais pas en contact avec le substrat ;

(V) appliquer une composition de silicone (X) sur la surface du substrat ou sur la surface de la couche par écoulement capillaire où la composition de silicone (X) est obtenue par un procédé comprenant la réaction :

(i) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs SiO_4/2 vaut de 0,05 à 4,0,

(ii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0,

(iii) un composé organosiloxane comprenant des motifs R²₃SiO_1/2, des motifs R¹SiO_3/2 et des motifs SiO_4/2, où le rapport molaire entre les motifs R²₃SiO_1/2 et les motifs R¹SiO_3/2 vaut de 0,05 à 3,0, et le rapport molaire entre les motifs R²₃SiO_1/2 et R¹SiO_3/2 combinés et les motifs SiO_4/2 vaut de 4 à 99,

(v) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R¹SiO_3/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R¹SiO_3/2 vaut de 0,2 à 4,0,

(vi) un composé organosiloxane comprenant des motifs R²₂SiO_2/2 et des motifs R²₃SiO_1/2, où le rapport molaire entre les motifs R²₂SiO_2/2 et les motifs R²₃SiO_1/2 vaut de 0 à 15 000, et
où R¹ est un groupe hydrocarbure dépourvu d'insaturation aliphatique et R² est choisi parmi R¹ et les groupes alcényle ;

(B) d'au moins un composé organohydrogénosilicium dans une quantité suffisante pour réticuler (A) choisi parmi

(VI) durcir la composition de silicone (X)
à condition que le rapport molaire entre les motifs R²₂SiO_2/2 et tous les autres motifs combinés soit plus élevé dans la composition de silicone (Y) que dans la composition de silicone (X), et que l'énergie de la surface de composition durcie (Y) soit inférieure à celle de la composition de silicone durcie (X) ; et

(VII) séparer la composition de silicone durcie (X) de l'étape (VI) du substrat.

Drawing

Cited references

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

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